KR20090115071A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to obtain a liquid crystal alignment film with high vertical alignment-regulating force, prevent display ununiformity when one drop fill mode is used in the manufacture of the vertical alignment type liquid crystal display device. CONSTITUTION: A liquid crystal alignment agent includes one or more polymers selected from the group consisting of polyamic acid and its imidized polymer. The polyamic acid is obtained by reacting tetracarboxylic dianhydride and diamine represented by chemical formula 1. In chemical formula 1, R is C3-20 alkyl group which can be substituted with a fluorine element; A is 1,4-cyclohexylene group or 1,4-phenylene group; B^1 is oxygen atom or -OCO-*, wherein a bonding hand attached with * is bonded with (CH2)b; B2 is oxygen atom or -OCO-*, wherein a bonding hand attached with * is bonded with A; a is 0 or 1; b is an integer of 2-10; and c is 0 or 1.

Description

Liquid crystal aligning agent and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, it relates to the liquid crystal aligning agent which provides the liquid crystal aligning film which does not produce ODF nonuniformity even when the liquid crystal dropping method (ODF system) is used in the liquid crystal filling process of manufacture of a liquid crystal display element, and the liquid crystal display element obtained therefrom.

Currently, as a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, polyimide, etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as the board | substrate for liquid crystal display elements, and the two sheets are opposed and arrange | positioned positively in the clearance gap. Having a layer of nematic liquid crystal having dielectric anisotropy to form a sandwich cell, and having a so-called twisted nematic liquid crystal cell in which the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other. TN type liquid crystal display elements are known. In addition, STN (Super Twisted Nematic) type liquid crystal display element, IPS (In-Plane Switching) type liquid crystal display element with low visual dependence, and VA (Vertical Alignment) type liquid crystal can realize higher contrast ratio than TN type liquid crystal display element. Optical compensation bend (OCB) type liquid crystal display devices have been developed that have a small display element and low visual dependence and are excellent in high-speed response of a video screen.

As a material of the liquid crystal aligning film in these liquid crystal display elements, although polyimide, polyamide, polyester, etc. are known conventionally, since polyimide is excellent in heat resistance, affinity with a liquid crystal, mechanical strength, etc., it is used for many liquid crystal display elements. have.

However, in recent years, the manufacturing process of the liquid crystal display device has made great progress. In particular, technologies such as a large substrate transfer technology and a liquid crystal dropping method (One Drop Fill method, abbreviated as "ODF method" in the art), which have been used with the enlargement of the substrate, are attracting attention. Among them, the ODF method is a method of dropping a liquid crystal onto a substrate on which a liquid crystal alignment film is formed, and bonding the liquid crystal to the other substrate in a vacuum, and then filling the entire surface of the panel with UV curing a sealing agent for sealing the liquid crystal. Compared with the vacuum injection method conventionally performed, it is a technique which can significantly shorten the process time of a liquid crystal filling process. However, when ODF method is used in manufacture of VA type liquid crystal display element which has a polyimide-type liquid crystal aligning film, the problem of display nonuniformity called "ODF nonuniformity" may arise. This phenomenon is considered to be due to the lack of the vertical alignment regulation force of the liquid crystal aligning film.

In order to solve this problem in the liquid crystal aligning film of a polyimide system, there exists a method of using the polyimide obtained using the diamine containing the diamine which has hydrophobic functional groups, such as a long-chain alkyl group, in high content rate (following patent) See references 1 and 2). Although this technique is an excellent technique by which the effect of raising a vertical alignment regulation force is expressed, the printability of a liquid crystal aligning agent may be impaired.

Therefore, the liquid crystal aligning agent which provides the liquid crystal aligning film which does not impair the various required performances especially which are required for a liquid crystal aligning agent, especially printability, and does not produce the said ODF nonuniformity, and the liquid crystal display element excellent in the display quality is calculated | required.

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-241646

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-305549

[Patent Document 3] Japanese Patent Application Laid-Open No. 9-278724

[Patent Document 4] Japanese Patent No. 2684404

[Patent Document 6] Japanese Unexamined Patent Publication No. 2002-327058

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal aligning film which exhibits a high vertical alignment regulating force in which display unevenness does not occur even when an ODF method is used in the manufacture of a VA type liquid crystal display element, and various performances required as liquid crystal aligning agents, in particular, It is providing the liquid crystal aligning agent excellent in printability, and the liquid crystal display element excellent in the display quality.

Still other objects and advantages of the present invention are apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are, firstly,

It is achieved by the liquid crystal aligning agent containing the at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing the compound represented by following formula (1), and its imidation polymer. .

In Formula 1, R is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A is a 1,4-cyclohexylene group or 1,4-phenylene group, and B ¹ is an oxygen atom or -OCO- ^* (Wherein the bond with "*" is bonded to (CH ₂ ) _b ), B ² is an oxygen atom or -COO- ^* (wherein the bond with "*" is bonded to A), a is 0 or 1, b is an integer from 2 to 10, c is 0 or 1)

The above objects and advantages of the present invention are second,

It is achieved by the liquid crystal display element provided with the liquid crystal aligning film formed from said liquid crystal aligning agent.

According to the present invention, it is possible to provide a liquid crystal aligning film which exhibits a high vertical alignment regulating force in which no display unevenness occurs even when an ODF method is used in the manufacture of a VA type liquid crystal display element, and various performances required as liquid crystal aligning agents, in particular, printing The liquid crystal aligning agent excellent in the characteristic and the liquid crystal display element excellent in the display quality can be provided.

The liquid crystal aligning agent of this invention contains the at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing the compound represented by the said Formula (1), and its imidation polymer. .

<Polyamic acid>

The polyamic acid which the liquid crystal aligning agent of this invention can contain can be synthesize | combined by making tetracarboxylic dianhydride and the diamine containing the compound represented by the said General formula (1) react.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid which the liquid crystal aligning agent of this invention can contain, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxyl Acid dianhydrides, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarb Acid dianhydrides, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuranthtetracar Acid dianhydrides, 1,3,3a, 4,5 , 9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1 , 3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naph Tol [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl- 5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxote Lahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracar Acid dianhydrides, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5 -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3 , 5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, represented by the following formulas TI and T-II, respectively Aliphatic or alicyclic tetracarboxylic dianhydrides such as compounds;

[Formula T-I]

[Formula T-II]

(In the above formula, R ¹ and R ³ each represent a divalent organic group having an aromatic ring, R ² and R ⁴ each represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ⁴ are the same or different, respectively. Can be)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride , p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (tri Phenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotri Mellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimelitate), 2,2-bis (4-hydroxyphenyl) propane- Aromatic tetracarboxylic dianhydride, such as a bis (anhydro trimellitate) and the compound represented by each of following General formula T-1-T-4, is mentioned. These are used individually by 1 type or in combination of 2 or more types.

[Formula T-1]

[Formula T-2]

[Formula T-3]

[Formula T-4]

The tetracarboxylic dianhydride used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain is the butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracar among the above. Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5 Tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride , 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetra Drofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8 , 10-tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride , 2,3 ', 2,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, among the compounds represented by the general formula TI to the following formula T-5 to At least one selected from the group consisting of a compound represented by each of T-7 and a compound represented by the above formula T-II, and a compound represented by the following formula T-8 (hereinafter, "specific tetracarboxylic acid (1) In the sense of including the "&quot; Is preferred.

[Formula T-5]

[Formula T-6]

[Formula T-7]

[Formula T-8]

As specific tetracarboxylic acid (1), 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride , 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the formula (T-5) At least one selected is preferred.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain is 20 mol of the specific tetracarboxylic dianhydride (1) based on the total tetracarboxylic dianhydride. It is preferable to contain% or more, It is more preferable to contain 50 mol% or more, It is preferable to contain especially 80 mol% or more.

[Diamine]

The diamine used for synthesize | combining the polyamic acid which the liquid crystal aligning agent of this invention can contain is the diamine containing the compound represented by the said General formula (1).

As R in the said Formula (1), it is preferable that it is a C3-C10 alkyl group, and it is more preferable that it is a C3-C10 linear alkyl group. It is preferable that b is an integer of 2-6. It is preferable that the diaminophenyl group of the left side of the said General formula (1) is a 2, 4- diamino phenyl group or a 3, 5- diamino phenyl group.

As a preferable example of the compound represented by the said General formula (1), the compound represented by each of following formula (1-1)-1-8 is mentioned, for example.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

(In Formulas 1-1 to 1-8, b is the same meaning as in Formula 1, d is an integer of 2 to 9)

The compound represented by the formula (1) can be synthesized by, for example, using a compound represented by the following formula (2) as a raw material and combining the methods of organic chemistry as appropriate.

(In Formula 2, R, A and c are the same meanings as in Formula 1, respectively.)

For example, the compounds represented by the above formulas 1-2, 1-3 and 1-7 can be synthesized by any of the following schemes 1 to 3, respectively. The compound represented by the said Formula (2) can be synthesize | combined by methods, such as the Grignard reaction, Friedel graft acylation reaction, and the Kisner reaction which are generally used for the synthesis | combination of a liquid crystalline compound.

(In Schemes 1 to 3, b and d have the same meanings as in the above Chemical Formulas 1-2, 1-3, or 1-7, respectively.)

Also about the other compound corresponding to the said Formula (1), it is possible to synthesize | combine according to the said method.

The liquid crystal aligning agent of the present invention, the connector for coupling with a structure represented by formula (2a) polymers - (CH _{2) b} - including (where, b is the same as defined in Formula 1, and the same hereinafter) In doing so, it became possible to express high vertical alignment regulation force.

(In Formula 2a, R and c each have the same meaning as in Formula 1)

As a technique using a structure similar to the structure of the formula (2a), the techniques described in Patent Document 3 (Japanese Patent Laid-Open No. 9-278724) and Patent Document 4 (Japanese Patent No. 2684404) are known, but the present invention The vertical alignment regulation force of the liquid crystal aligning film formed from the liquid crystal aligning agent of is beyond these conventional techniques. This is presumably because the structure of the above formula (2a) is largely involved in the expression of the vertical alignment regulating force, and this is because it appears on the surface of the liquid crystal alignment film through-(CH ₂ ) _b -with high flexibility.

The diamine used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain may be a diamine containing only the compound represented by the formula (1), or further diamine other than the compound represented by the formula (1) It may be included.

As another diamine which can be used here, for example, p-phenylenediamine, m-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenylethane, 4,4'- Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'- Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2, 2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'- Aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether, 3,3 '-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9, 9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5 '-Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4, 4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4 Aromatic diamines such as' -bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylene Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -unde Aliphatic or alicyclic diamines such as silendimethyldiamine and 4,4'-methylenebis (cyclohexylamine);

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Aminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, a compound represented by the following formula DI, a compound represented by the following formula D-II and the like Diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in the molecule of;

[Formula D-I]

In formula DI, R ⁵ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X ¹ represents a divalent organic group, and R ⁶ represents an alkyl group having 1 to 4 carbon atoms, a1 represents an integer of 0 to 3)

[Formula D-II]

In Formula D-II, R ⁷ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X ² each represents a divalent organic group And a plurality of X ^{2 's} may be the same or different, and each R ⁸ represents an alkyl group having 1 to 4 carbon atoms, and a2 each represents an integer of 0 to 3).

Mono-substituted phenylenediamines represented by the following formula (D-III);

[Formula D-III]

In formula D-III, R ⁹ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R ¹⁰ represents a steroid skeleton, trifluoro A monovalent organic group having a group selected from a romethylphenyl group, a trifluoromethoxyphenyl group and a fluorophenyl group or an alkyl group having 6 to 30 carbon atoms, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, and a3 represents 0 to 3 Represents an integer)

Diaminoorganosiloxane represented by the following formula (D-IV);

[Formula D-IV]

(In formula (D-IV), R <^12> represents a C1-C12 hydrocarbon group each, two or more R <^12> may be same or different, respectively, s is an integer of 1-3, t is a 1-20 Integer)

The compound etc. which are represented by each of following formula D-1-D-5 are mentioned.

[Formula D-1]

[Formula D-2]

[Formula D-3]

[Formula D-4]

[Formula D-5]

(Y in Formula D-4 is an integer of 2-12, z in Formula D-5 is an integer of 1-5)

The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). R ⁶ , R ⁸ and R ¹¹ in Formulas DI, D-II and D-III are each preferably a methyl group, and a1, a2 and a3 are each preferably 0 or 1, and more preferably 0. Do.

When synthesize | combining the polyamic acid which may be contained in the liquid crystal aligning agent of this invention, the other diamine used together with the compound represented by the said General formula (1) is p-phenylenediamine, 4,4'- diamino among the above-mentioned things. Diphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoro Methyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Lopropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'- Methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, A compound represented by each of the formulas D-1 to D-5, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, a compound represented by the following formula D-6 among the compounds represented by the formula (DI), a compound represented by the following formula D-7 among the compounds represented by the formula (D-II) And dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy, among the compounds represented by Formula D-III. -2,5-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2 , 5-diaminobenzene and the following formula D-8 to It is preferable to include one or more types (hereinafter, referred to as "other specific diamines") selected from the group consisting of compounds represented by each of D-16.

[Formula D-6]

[Formula D-7]

[Formula D-8]

[Formula D-9]

[Formula D-10]

[Formula D-11]

[Formula D-12]

[Formula D-13]

[Formula D-14]

[Formula D-15]

[Formula D-16]

The diamine used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain contains preferably 1 mol% or more of the compound represented by the formula (1) with respect to all diamines, and contains 5 to 50 mol%. It is more preferable, and it is preferable to contain 10-40 mol% especially.

The diamine used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain contains, in addition to the compound represented by the above formula (1), 5 to 95 mol% of other specific diamines as described above with respect to the total diamine. It is preferable, it is more preferable to contain 20-90 mol%, and it is especially preferable to contain 50-90 mol%.

Since the liquid crystal aligning agent of this invention can provide the liquid crystal aligning film which has at least the favorable vertical alignment regulation force of the use ratio of the compound represented by the said Formula (1) in the diamine used for synthesize | combining the polymer contained in this, a liquid crystal The printability of the alignment agent and the vertical alignment regulation force of the liquid crystal alignment film can be made compatible. In the present invention, even when the use ratio of the compound represented by the formula (1) in the diamine is 40 mol% or less, more preferably 30 mol% or less, in particular 20 mol% or less, the liquid crystal alignment film formed is excellent. Vertical orientation regulation force.

[Synthesis of Polyamic Acid]

The polyamic acid which the liquid crystal aligning agent of this invention can contain can be obtained by making tetracarboxylic dianhydride and diamine as mentioned above react.

The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is the ratio which becomes 0.3 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 1 to 240 hours, more preferably 3 to 150 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphoramide; and phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. In addition, as for the usage-amount of organic solvent (a: However, when using together an organic solvent and the poor solvent mentioned later, the total amount thereof), the total amount (b) of tetracarboxylic dianhydride and a diamine compound is a It is preferable that it is an amount which will be 0.1-30 weight% with respect to whole quantity (a + b).

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acids, can be used in combination without causing precipitation of the resulting polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, lactic acid Butyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, di Ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Recol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o -Dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, iso amyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.

When using an organic solvent and a poor solvent together when synthesize | combining a polyamic acid, the use ratio of the poor solvent becomes like this. Preferably it is 80 weight% or less, More preferably, it is 60 weight% or less with respect to the sum total of an organic solvent and a poor solvent, More preferably, it is 50 weight% or less.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or the method of distilling a reaction solution under reduced pressure with an evaporator. Moreover, polyamic acid can be refine | purified by the method which melt | dissolves this polyamic acid again in an organic solvent, and then precipitates with a poor solvent, or performs the process of distilling off under reduced pressure with an evaporator once or several times.

[Imidated Polymer]

The imidation polymer which can be contained in the liquid crystal aligning agent of this invention can be obtained by imidating by dehydrating and ring-closing the polyamic acid as mentioned above.

As tetracarboxylic dianhydride used for the synthesis | combination of an imidation polymer, 1 or more types (it is called "a specific tetracarboxylic dianhydride (2)" hereafter) chosen from alicyclic tetracarboxylic dianhydride are included. It is preferable to use tetracarboxylic dianhydride. As specific tetracarboxylic dianhydride (2), 2,3,5- tricar carboxycyclopentyl acetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2) , 5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4- Dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride, 3,5,6-tricarboxy- ^2- carboxynorbornane-2: 3,5: 6-dianhydride and 4,9-dioxatricyclo [5.3.1.0 ^{2 , 6} ] at least one member selected from the group consisting of undecane-3,5,8,10-tetraone is preferred.

The tetracarboxylic dianhydride used for synthesizing the imidized polymer which the liquid crystal aligning agent of the present invention may contain may contain specific tetracarboxylic dianhydride (2) as described above with respect to the total tetracarboxylic dianhydride. It is preferable to contain mol% or more, It is more preferable to contain 50 mol% or more, It is preferable to contain 80 mol% or more especially.

As diamine used for the synthesis | combination of the said imidation polymer, the diamine same as the diamine used for the synthesis | combination of the polyamic acid mentioned above is mentioned.

The imidized polymer may be a complete imide compound in which all of the amic acid structures possessed by the polyamic acid as a raw material are dehydrated and closed, and only a part of the amic acid structure is dehydrated and closed, so that the amic acid structure and the imide ring structure coexist. It may be an imide.

It is preferable that the imidation ratio of the imidation polymer contained in the liquid crystal aligning agent of this invention is 30% or more, and it is especially preferable that it is 50%.

The said imidation ratio shows the ratio which the number of the imide ring structures to the sum total of the number of the amic acid structures and the number of imide ring structures of an imidation polymer occupies as a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation ratio is obtained by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference substance. Can be obtained by

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100

(In Formula 1, A ¹ is the peak area derived from the proton of the NH group which appears near 10 ppm of chemical shift, A ² is the peak area derived from the other proton, and α is a precursor of the imidized polymer (polyamic acid Is ratio of number of other protons to one proton of NH group in

The dehydration ring closure of the polyamic acid for synthesizing the imidized polymer may be performed by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring closure catalyst in the solution. By heating as necessary.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall. The reaction time is preferably 0.5 to 24 hours, more preferably 2 to 12 hours.

As a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, and a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, as an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 2 to 8 hours.

The imidation polymer obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the imidation polymer obtained. On the other hand, in the said method (ii), the reaction solution containing an imidation polymer is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, and after the imidation polymer is isolated, for the preparation of the liquid crystal aligning agent. It may be used, or may be used for the production of a liquid crystal aligning agent after purifying the isolated imidized polymer. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of the imidized polymer can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

Terminal Modified Polymer

The polyamic acid or imidation polymer thereof which the liquid crystal aligning agent of the present invention may contain may be a terminal modified form in which molecular weight is controlled. By using the polymer of the terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such a terminal-modified polymer can be performed by adding a molecular weight modifier to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. have. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc. are mentioned. As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

The use ratio of the molecular weight modifier is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

Solution viscosity

The polyamic acid or the imidized polymer obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, and more preferably a solution viscosity of 30 to 500 mPa · s when the solution has a concentration of 10% by weight. desirable.

The solution viscosity (mPa · s) of the polymer is a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

<Other additives>

Although the liquid crystal aligning film of this invention contains as an essential component 1 or more types of polymers chosen from the group which consists of the polyamic acid mentioned above and the imidation polymer formed by dehydrating and ring-closing this as an essential component, you may contain other components as needed. Examples of such other components include compounds having one or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound"), functional silane compounds, and the like.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5 , 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycid Diyl-aminomethylcyclohexane etc. are mentioned as a preferable thing. The proportion of these epoxy group-containing compounds is preferably 40 parts by weight or less, more preferably 40 parts by weight or less based on 100 parts by weight of the total amount of the polymer (the total amount of the polyamic acid and its imidized polymer contained in the liquid crystal aligning agent, which is the same below). Preferably from 0.1 to 30 parts by weight.

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-acea Nopropyltriethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane etc. are mentioned.

The compounding ratio of these functional silane containing compounds becomes like this. Preferably it is 40 weight part or less with respect to 100 weight part of total amounts of a polymer.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of the present invention preferably comprises one or more polymers selected from the group consisting of polyamic acid and imidized polymers thereof as described above, and other additives optionally blended as needed, preferably dissolved in an organic solvent. do.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together. Preferred examples of such organic solvents include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol -n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol di Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, And the like can be mentioned isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether. These may be used independently, or may mix and use 2 or more types.

The solid content concentration (the ratio of the total weight of the components except the organic solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) of the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, but preferably 1 To 10% by weight. That is, although the coating film which becomes a liquid crystal aligning film is formed by apply | coating this to the surface of a board | substrate and removing an organic solvent, when the solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal In some cases, it may be difficult to obtain an alignment film, and on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film may be too large to obtain a good liquid crystal alignment film in the same manner, and the viscosity of the liquid crystal aligning agent may be increased to apply the coating. A characteristic may fall.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% is especially preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and the solution viscosity is in the range of 3 to 15 mPa · s.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent of this invention. It is preferable that the liquid crystal display element of this invention is a vertical alignment type liquid crystal display element which has a liquid crystal cell of a vertical alignment type.

The liquid crystal display element of this invention can be manufactured by the following method, for example.

(1) The liquid crystal aligning agent of this invention is apply | coated to one side of the board | substrate with which the patterned transparent conductive film is provided by methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, and then, a coating surface is heated. This forms a coating film. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate containing plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be used. In order to obtain a patterned transparent conductive film, a method of forming a desired pattern by photoetching after forming a transparent conductive film without a pattern on a substrate, for example, when forming a transparent conductive film, a transparent conductive patterned using a mask having a desired pattern The method of forming a film directly can be used. At the time of application | coating of a liquid crystal aligning agent, in order to make adhesiveness of the liquid crystal aligning film formed and a surface of a board | substrate more favorable, you may apply | coat a functional silane compound, a functional titanium compound, etc. previously on a board | substrate, for example. Preliminary heating (prebaking) is performed for the purpose of liquid dripping prevention of the aligning agent apply | coated after liquid crystal aligning agent application | coating. Preliminary baking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. The preliminary baking time is preferably 0.5 to 10 minutes, more preferably 1 to 5 minutes. Thereafter, a firing (post-baking) step is performed for the purpose of completely removing the solvent. Thereafter, the baking temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. Post-baking time becomes like this. Preferably it is 5-180 minutes, More preferably, it is 10-120 minutes.

Although the liquid crystal aligning agent of this invention forms the coating film used as an orientation film by removing an organic solvent after application | coating, the polymer contained in the liquid crystal aligning agent of this invention is an imidized polymer which uses a polyamic acid or an imide ring structure, and an amic acid structure together. In this case, by further heating after coating film formation, a dehydration ring-closure reaction is advanced and it can also be set as the imidized coating film.

The film thickness of the coating film formed here becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as above-mentioned, and arrange | positioning a liquid crystal between these two board | substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other with a gap (cell spacing) so that each liquid crystal alignment film faces each other, and the two substrate peripheries are bonded using a sealant, and the cell gap partitioned by the substrate surface and the sealant. After injecting and filling a liquid crystal in the inside, a liquid crystal cell can be manufactured by sealing an injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet photocurable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and after dropping the liquid crystal onto the liquid crystal alignment film surface, the other substrate is bonded to face the liquid crystal alignment film. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent. Since the liquid crystal aligning agent of this invention can form the liquid crystal aligning film excellent in the vertical alignment property, it has the advantage that the liquid crystal display element which ODF nonuniformity does not generate | occur | produce even when a VA type liquid crystal display element is manufactured by ODF method is obtained. .

Also by any method, it is preferable to remove the liquid orientation at the time of liquid crystal filling by heating a liquid crystal cell to the temperature which the liquid crystal used subsequently takes an isotropic phase, and then gradually cooling to room temperature.

Moreover, the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell.

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Especially, the nematic type liquid crystal which has negative dielectric anisotropy is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenylcyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenylcyclo Hexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, these liquid crystals are, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). You can also use it, adding the chiral agent etc. which are sold. In addition, ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned. have.

<Example>

<Synthesis of Compound Represented by Formula 1>

Example 1 (Synthesis of Compound (1-2-1))

According to Scheme 4 below, compound (1-2-1) was synthesized.

Synthesis of Compound (1-2-1b)

66 g of compound (1-2-1a), 61 g of potassium carbonate, 27 g of iodineethanol and 300 mL of 1-methyl-2-pyrrolidone were charged into a 1 L three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer. And reaction was performed at 100 degreeC for 5 hours. After the reaction was completed, the reaction mixture was poured into 1.5 L of water, and the resulting precipitate was recovered. The solution obtained by dissolving this precipitate in ethyl acetate was washed three times with water, dried over magnesium sulfate, concentrated, and the solvent was removed to give 72 g of a compound (1-2-1b).

Synthesis of Compound (1-2-1c)

Into a 1 L three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, 56 g of compound (1-2-1b), 17 g of t-butoxy potassium, 4.8 g of tetrabutylammonium bromide and 400 mL of tetrahydrofuran were added thereto. The mixture was cooled with ice and stirred for 3 hours (this was referred to as reaction solution A).

Meanwhile, 30 g of 2,4-dinitrochlorobenzene and 30 mL of tetrahydrofuran were added to a 1 L three-necked flask equipped with a dropping funnel, a nitrogen inlet tube, and a stirrer, and the reaction solution A was cooled for 1 hour or more. It was dripped gradually over and reaction was performed at room temperature for 12 hours as it was. After the reaction was completed, the reaction mixture was poured into 1 L of water, and the resulting precipitate was recovered. The solution obtained by dissolving this precipitate in ethyl acetate was washed three times with water, dried over magnesium sulfate, concentrated and recrystallized with ethanol to obtain 65 g of compound (1-2-1c).

Synthesis of Compound (1-2-1)

Into a 2 L three-necked flask equipped with a reflux tube, a nitrogen inlet tube, and a thermometer, 54 g of Compound (1-2-1c), 226 g of tin chloride dihydrate, and 1 L of ethyl acetate were added and reacted under reflux for 4 hours. It was. After completion of the reaction, an aqueous potassium fluoride solution was added to the reaction mixture, and the resulting precipitate was removed by filtration, followed by separating an aqueous layer to obtain an organic layer. The organic layer was washed sequentially with aqueous potassium fluoride solution and water, dried over magnesium sulfate, concentrated and recrystallized with ethanol to obtain 36 g of compound (1-2-1).

Example 2 (Synthesis of Compound (1-7-1))

According to Scheme 5 below, compound (1-7-1) was synthesized.

Synthesis of Compound (1-7-1b)

In a 1 L three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 81 g of compound (1-7-1a), 60 g of succinic anhydride, 4.4 g of N, N-dimethylaminopyridine, 36 g of triethylamine and ethyl acetate 400 mL was added and reaction was performed at 90 degreeC for 8 hours. After completion of the reaction, ethyl acetate was distilled off from the reaction mixture, and 2 L of chloroform was added to the residue to obtain an organic layer. The organic layer was washed three times with dilute hydrochloric acid and four times with water. The organic layer was dried over magnesium sulfate, concentrated, and the resulting precipitate was collected by filtration and dried to obtain 97 g of compound (1-7-1b). .

Synthesis of Compound (1-7-1c)

In a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 74 g of compound (1-7-1b), 43 g of 3,5-dinitrobenzylchloride, 83 g of potassium carbonate, 60 g of sodium iodide and N, 500 mL of N-dimethylformamide was added thereto, and the reaction was carried out at 60 ° C. for 8 hours. After the reaction was completed, 3 L of chloroform was added to the reaction mixture, and the organic layer was washed three times with water. Subsequently, after drying with magnesium sulfate with respect to the organic layer, it concentrated and collect | recovered the precipitated solid, wash | cleaned with ethanol, and ethanol was removed under reduced pressure, and 88 g of compounds (1-7-1c) were obtained.

Synthesis of Compound (1-7-1)

82 g of compound (1-7-1c), 340 g of tin chloride dihydrate, and 1 L of ethyl acetate were added to a 2 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and the reaction was performed under reflux for 4 hours. . After completion of the reaction, an aqueous potassium fluoride solution was added to the reaction mixture, and the precipitate was removed by filtration, followed by separating an aqueous layer to obtain an organic layer. The organic layer was washed sequentially with an aqueous potassium fluoride solution and water, dried over magnesium sulfate, concentrated and recrystallized with ethanol to obtain 50 g of compound (1-7-1).

<Synthesis of imidized polymer>

Example 3

61 g of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic anhydride, 13 g of compound (1-2-1) as diamine (equivalent to 0.1 mole per mole of TCA) and A solution containing 20% by weight of polyamic acid was obtained by dissolving 26 g of p-phenylenediamine in 400 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 6 hours. About this solution, the solution viscosity measured at 25 degreeC was 6,000 mPa * s.

Subsequently, 1,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 21 g of pyridine and 28 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone (by this solvent substitution operation, the pyridine and acetic anhydride used for the dehydration ring closure reaction were removed out of the system, which is the same below). The solution containing 20 weight% of imidation polymers (A-1) of about 50% of imidation ratios was obtained. A small amount of this solution was added, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having an imidized polymer concentration of 6.0% by weight was 25 mPa · s.

Example 4

61 g of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic anhydride, 13 g of compound (1-7-1) as diamine (equivalent to 0.1 mole per 1 mole of TCA) and A solution containing 20% by weight of polyamic acid was obtained by dissolving 26 g of p-phenylenediamine (PDA) in 400 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 6 hours. About this solution, the solution viscosity measured at 25 degreeC was 4,800 mPa * s.

Subsequently, 1,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 21 g of pyridine and 28 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidization polymer (A-2) having an imidization ratio of about 50%. A small amount of this solution was added, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having an imidized polymer concentration of 6.0% by weight was 22 mPa · s.

<Comparative Synthesis Example of Imidized Polymer>

Comparative Synthesis Example 1

29 g of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic anhydride and 9.9 g of a compound represented by the following general formula R-1 as diamine (corresponding to 0.2 mole per mole of TCA) And 11 g (PDA) of p-phenylenediamine were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. About this solution, the solution viscosity measured at 25 degreeC was 3,500 mPa * s.

[Formula R-1]

Subsequently, 500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 10 g of pyridine and 13 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidization polymer (B-2) having an imidation ratio of about 49%. A small amount of this solution was added, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having an imidized polymer concentration of 6.0% by weight was 25 mPa · s.

<Production and Evaluation of Liquid Crystal Alignment Agent>

Example 5

[Production of liquid crystal aligning agent for printability evaluation]

100 weight part of the imidation polymer (A-1) which contains the compound represented by following formula (E-1) as an epoxy compound in the said solution in the solution containing the imidation polymer (A-1) obtained in the said Example 3 20 parts by weight of the solvent was added, and γ-butyrolactone (BL), N-methyl-2-pyrrolidone (NMP), and butyl cellosolve (BC) were added, and the solvent composition was BL: NMP: BC = 40: 30: 30 (weight ratio) and solid content concentration were made into the solution of 6.0 weight%. The liquid crystal aligning agent for printability evaluation was manufactured by filtering this solution using the filter of 1 micrometer of pore diameters. About this liquid crystal aligning agent, the solution viscosity measured at 25 degreeC was 22 mPa * s.

[Formula E-1]

[Evaluation of Printability]

About the liquid crystal aligning agent for printability evaluation manufactured above, the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film | membrane using a liquid crystal aligning film printer (Nipbon Shashin Insatsu Co., Ltd., Angstromr S40L-532). After coating, the solvent was removed by heating (pre-baking) at 80 ° C for 1 minute and then heating (post-baking) at 180 ° C for 10 minutes to form a coating film having a film thickness of 8,000 nm. When the coating film was visually observed and examined for the presence of cratering and coating unevenness, neither printing unevenness nor pinhole was observed, and the printability of the liquid crystal aligning agent was "good."

[Production of Liquid Crystal Alignment Agent for Liquid Crystal Display Device Production]

100 parts by weight of the imidized polymer (A-1) containing the compound represented by the formula (E-1) as an epoxy compound in the solution in the solution containing the imidized polymer (A-1) obtained in Example 3 20 parts by weight of the solvent was added, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added, and the solvent composition was NMP: BC = 50: 50 (weight ratio), and the solid content concentration was It was set as the solution which is 4 weight%. The liquid crystal aligning agent for liquid crystal display element manufacture was manufactured by filtering this solution using the filter of 1 micrometer of pore diameters.

[Manufacture of Liquid Crystal Display Element for Vertical Orientation Regulatory Force Evaluation]

The above-mentioned liquid crystal aligning agent for liquid crystal display element manufacture was apply | coated with a spinner on the transparent conductive film containing the ITO film | membrane provided in one side of the glass substrate of thickness 1mm, and it heats at 80 degreeC on a hotplate for 1 minute (prebaking) ), The solvent was removed, and then heated (post-baked) at 200 ° C. for 60 minutes to form a coating film having a thickness of 0.08 μm. About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound up the rayon spring at roll rotation speed 400rpm, stage movement speed 3cm / sec, and hairpin indentation length 0.4mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 230 ° C clean oven for 25 minutes to obtain a substrate having a liquid crystal alignment film subjected to a rubbing treatment. This operation was repeated and a pair (two sheets) of the board | substrates which have a liquid crystal aligning film which performed the rubbing process were obtained.

Subsequently, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to each outer edge which has the liquid crystal aligning film of the said pair of board | substrates, it overlaps and crimps so that a liquid crystal aligning film surface may become antiparallel, and hardens an adhesive agent I was. Subsequently, after filling a nematic liquid crystal (MLC-6608, Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, a liquid crystal injection hole is sealed with an acryl-type photocuring adhesive agent, and it is set as a liquid crystal cell, and a polarizing plate is formed on the outer both sides of this liquid crystal cell. The liquid crystal display element for evaluation of vertical orientation regulation force was manufactured by bonding.

[Evaluation of Vertical Orientation Regulatory Force]

For the liquid crystal display device for evaluating the vertical alignment regulating force, the pretilt angle measured by the crystal rotation angle method was 86 ° or more, and the vertical alignment regulating force "good" and less than 86 ° were evaluated as vertical orientation regulating force "bad". This liquid crystal display device showed a pretilt angle of 89 °, and the vertical alignment regulating force was "good."

Moreover, it is known that the rubbing process performed by the said "manufacturing of the liquid crystal display element for vertical orientation regulation force evaluation" has the effect of reducing the vertical orientation regulation force of a liquid crystal aligning film. In addition, even though the rubbing treatment was performed, when the pretilt angle of 86 ° or more was exhibited, the vertical alignment regulating force was very excellent, and the liquid crystal aligning agent providing such a result was a VA type liquid crystal display device using the ODF method. It is empirically clear that the display unevenness does not occur even when used in the preparation of the.

[Manufacture of Liquid Crystal Display Element for Voltage Retention Rate Evaluation]

In the above-mentioned [Manufacture of liquid crystal display element for vertical alignment force evaluation], it carried out similarly to the above [Manufacturing of liquid crystal display element for vertical orientation force evaluation] except having not performed the rubbing process and then wash | cleaning and drying process with respect to the formed coating film. It carried out and manufactured the liquid crystal display element for voltage retention evaluation.

[Evaluation of Voltage Retention Rate]

For the liquid crystal display device for voltage retention evaluation prepared above, after applying a voltage of 5 V at 60 ° C. with a span of 60 microseconds and a span of 16.7 microseconds, the voltage 16.7 milliseconds after the release of voltage application was applied. Retention rate was measured. The voltage retention of this liquid crystal display element was 99%.

Example 6 and Comparative Example 1

In the said Example 5, except having used the solution containing the imidation polymer shown in Table 1 as a solution containing an imidation polymer, it carried out similarly to Example 5, and manufactured and evaluated each 2 types of liquid crystal aligning agents. The evaluation result was shown in Table 1 with the solution viscosity of the liquid crystal aligning agent for printability evaluation.

As specifically explained by the above examples, the liquid crystal aligning agent of the present invention exhibits excellent printability and the liquid crystal aligning film formed therefrom has a good vertical alignment regulating force. Even when the device is manufactured, there is an advantage that a liquid crystal display device in which ODF nonuniformity does not occur can be manufactured with high yield.

Claims (4)

It contains a polyamic acid obtained by reacting tetracarboxylic dianhydride and a diamine containing a compound represented by the following formula (1) and at least one polymer selected from the group consisting of imidized polymers thereof. . <Formula 1>

In Formula 1, R is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A is a 1,4-cyclohexylene group or 1,4-phenylene group, and B ¹ is an oxygen atom or -OCO- ^* (Wherein the bond with "*" is bonded to (CH ₂ ) _b ), B ² is an oxygen atom or -COO- ^* (wherein the bond with "*" is bonded to A), a is 0 or 1, b is an integer from 2 to 10, c is 0 or 1) The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 1 is provided, The liquid crystal display element characterized by the above-mentioned. Polyamic acid or imidation polymer obtained by making tetracarboxylic dianhydride and the diamine containing the compound represented by following formula (1) react. <Formula 1>

In Formula 1, R is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A is a 1,4-cyclohexylene group or 1,4-phenylene group, and B ¹ is an oxygen atom or -OCO- ^* (Wherein the bond with "*" is bonded to (CH ₂ ) _b ), B ² is an oxygen atom or -COO- ^* (wherein the bond with "*" is bonded to A), a is 0 or 1, b is an integer from 2 to 10, c is 0 or 1) A compound represented by the following formula (1). <Formula 1>

In Formula 1, R is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A is a 1,4-cyclohexylene group or 1,4-phenylene group, and B ¹ is an oxygen atom or -OCO- ^* (Wherein the bond with "*" is bonded to (CH ₂ ) _b ), B ² is an oxygen atom or -COO- ^* (wherein the bond with "*" is bonded to A), a is 0 or 1, b is an integer from 2 to 10, c is 0 or 1)